Condensation products and a process of preparing them



Patented Nov. 21, 1939 OONDENSATION PRODUCTS AND A PROCESS OF PREPARINGTHEM amine Brunner, Frankfort-on-the-Main, Germany, asaignorto I. G.Farbenindustrle Ak- .tiengeseibchaft, Frankfort-on-the-Main, Ger- NoDrawing. Original application February 26,

1937, Serial No. 128,035. Divided and this application-October 12, 1937,Serial No. 168,681. r In Germany March 5. 1936 5 Claims. (am-291;

The present invention relates to condensation products and to a processof preparing them.

This application is a division of United States patent application Ser.No.-128,025, filed Feb- 5 ruary 26, 1937, in the name of Arnold Brunnerfor Condensation products and a process of preparing them.

I have found that chloromethyl groups may be introduced into suchphenols as contain in the m nucleus one o'rmore long aliphatic chainshaving at least 4 carbon atoms, as, for instance, butylor octylphenol,by a treatment with aqueous formaldehyde solutions saturated withhydrochloric acid, advantageously at a temperature between 50 C and 100C. This could not be foreseen;

it was rather to be expected that the reactivity of the phenols would bedim nished too much by long aliphatic radicals or that the reactionwould occur in quite another manner. V The chloromethylcompoundsobtained correspond with the following general formula:

wherein A(OH) means the radical of an aromatic hydroxyl compound, Rmeans an aliphatic radical containing at least 4 carbon atoms, and arevisallow a variety of reactions on account of the exchangeable chlorineatom and are valuable intermediates for the preparation of dyestuffs,artiflcial resins, tanning agents, auxiliary agents in the dyeingindustry and other products.

Furthermore, I have found that the condensatlon products, obtainable bytreating phenols containing aliphatic side chains having at least 4carbon atoms with aqueous formaldehyde solutions saturated withhydrochloricacid, may be caused to react with organic nitrogen bases,which may also contain acid groups (for instance, sulfo groups), withformation of new condensation products containing nitrogen. Thereactions,

which occur with evolution of heat, may be carried out in the presenceor absence of a solvent at ordinary or raised temperature(advantageously at a temperature up to about 100 (2.). If suitablesolvents are used, the products precipitate in some cases, so that theymay be separated from the mother-liquor. The aqueous solutions. of the 9products, n s a a do n t c nta n acid bases contain the group which hasthe formula: 1

. N\ Ci Cl wherein N represents the nitrogen atom of an organic base,'A(OH) means the radical of an aromatic hydroxyl compound and .R'meansan aliphatic radical having at least 4 carbon atoms.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto; the parts are by weight:

(1) Into a solution of 24 parts of paraformaldehyde in 400 parts ofstrong hydrochloric acid there is introduced at C. hydrochloric acid gasuntil the solution is. saturated and at the same temperature there areadded in the course of 4 hours, while well stirring, 41 parts oftechnical isooctyl-phenol, advantageously in the molten state. Duringthe addition of isooctyl-phenol and for a short time thereafter. thereis conducted a feeble current of hydrochloric acidgas through v thesolution. I

The resinous products are separated from the mother liquor and eitherdried with precaution under reduced pressure or isolated by dissolutionin an organic solvent, drying by means of calcium chloride anddistillation ofthe solvent. It contains about 15 per cent. of chlorine(calculated: 13.95 per cent. of chlorine on entrance of one chloromethylgroup and 23.43 per cent. of chlorine on entrance of two groups) Thebrownishcolored viscous resinous mass is soluble in ether. and.

other organic solvents, and difllcultly soluble in water.

(2)) Hydrochloric acid gas is conducted at 60 C. into a mixtureconsisting of 120 parts of para-formaldehyde and 1300 parts of stronghydrochloric acid until the solution is saturated and, at the sametemperature, 142 parts of isobutylphenol are added in the course of 4hours. After having introduced hydrochloric acid gas at 60 C. for aboutfurther 8 hours, the whole is worked up as described in Example 1.

The brownish syrupy product soluble in organic solvents and difllcultlysoluble in water. contains 17.84 per cent. of chlorine (calculated:1.7;88 per cent. on entrance of one chloromethyl group).

.(3) Hydrochloric acid gas is conducted for 24 hours in a mixtureconsisting of 12 parts of paraiformaldehyde, 300 parts of stronghydrochloric acid and 51 parts of diisooctyl-phenol while raising thetemperature gradually from 50C. to 90 C. The product is worked up asdescribed in- Examples 1 and 2. The analysis shows 8.52 per cent. ofchlorine (calculated on the entrance of one chloromethyl group 9.69 percent. of chlo rine) The product is a viscous brownish resinous mass,which is diflicultly soluble in water and easily soluble in organicsolvents.

(4) By using 160 parts of isododecyl-phenol, 1200 parts of hydrochloricacid and 80 parts of para-formaldehyde there is obtained in the courseof 15 hours while heating at 50 C., a product which contains 129 percent. of chlorine (calculated 11.43 per cent.). It is of brownish color.viscous, diihcultly'soluble in water and easily soluble in organicsolvents.

(5) 57 parts of isobutylisooctyl-phenol yield on heating at C. for 20hours with 400 parts of hydrochloric acid and 12 parts ofpara-formaldehyde a product containing 12.25 per cent. of chlorine(calculated 11.70 per cent.). The physical properties of the productcorrespond with those of the product obtained according to Example 3.

(6) From 105 parts of n-dodecyl-phenol there is obtained with 1000 partsof hydrochloric acid and 50 parts of para-formaldehyde in the course of10 hours while heating at 50 C. a product containing 9.5 per cent ofchlorine.

('7) By using a technical mixture from isododecyl-, isotridecylandisotetradecyl-phenol, there are obtained products the content ofchicrine of which lies between about 10 and about 12 per cent.

(8) 20 parts of the chloromethyl compound of isobutyl-phenol themanufacture of which is described in Example 2, are dissolved in 60parts of soluble in water or alcohol, hardly soluble in ben- Zane,acetone or petroleum ether.

(9) '4 parts of the chloromethyl compound of isododecyl-phenol themanufacture oi. which is described in Example 4, are dissolved in 10parts of acetone and 4 parts of pyridine are added;

self-heating occurs. After boiling for two hours.

in a reflux apparatus, the acetone and. the pyridinein excess aredistilled and a yellowish visous resinous mass is obtained which isreadily g i leginwater and aicohotjless readily soluble in benzene oracetone and more difncultly soluble in ligroin.

A weak aqueous solution, of about 121000, shows in an especially highdegree a peculiarity which is shared also, but in most cases in a lessmarked degree, by the products of the other examples: namely, when sucha solution, which is by no means viscous, is heated nearly to boiling ina glass vessel, the bubbles formed cling to the walls and do not rise orrise only slowly.

(10) 116 parts of the chloromethyl compound of isooctyl-phenol themanufacture of which is described in Example 1, are heated with 116parts of pyridine, for about one hour to water-bath temperature. Thepyridine in excess is then distilled (most advantageously under reducedpressure). The yellowish resinous residue is watersoluble.

(11) 6 parts of the chloromethyl compound of dodecyl-phenol, themanufacture of which is described in Example 4, are dissolved in 60parts of petroleum ether. While stirring and cooling, the solution isrun into a solution of 6 parts of tri-ethylamine in 20 parts ofpetroleum ether. The product is then filtered with suction and driedunder reduced pressure. It forms a solid resinous substance of feeblyyellowish .color which is readily soluble in water and alcohol, lessreadily soluble in benzene and difllcultly soluble in ligroin. v

(12) 10 parts of the chloromethyl compound of diisooctyl-phenol, themanufacture of which is described in Example 3, are dissolved in 30parts of petroleum ether. After addition of 10 parts of pyridine heat isdeveloped, but no precipitation occurs. After distilling the solvent ayellowish resinous mass is obtained which is easily soluble inorganic-solvents, but only sparingly in water. Its alcoholic solution ofabout 10 per cent. strength may be diluted with any amount of waterwithout producing precipitation.

(13) 62 parts of the chloromethyl compound of dodecyl-phenol, themanufacture of which is described in Example 4, are dissolved in 100parts of alcohol and 22 parts of methyl-aniline are added. The reactiondevelops heat. The whole is boiled under reflux for about one hour, andsuch an amount of alcohol is added, that a solution of about 10 percent. strength is formed. This solution may be diluted with any amountof water; advantageously it is run, while stirring, into the desiredamount of water. Ahomogeneous, lacteal-colloidially turbid solution isobtained.

(14) By using in Example 13 20 parts of aniline instead of 22 parts ofmethyl-aniline, a product is obtained, which may be worked up in thesame manner as that described in Example 13 and possesses similarproperties.

15) 11.8 parts of the chloromethyl compound of isooctyl-phenol, themanufacture of which is described in Example 1, are dissolved in 30parts of dioxane. The solution is added to a solution of 10 parts ofsodium sulfanilate in 15 parts of water, whereby heat is generated.After stirring for a short time, 2.7 parts of sodium carbonate are addedand stirring is continued for some hours, until the mass has becomehomogeneous (18) 27.! parts of the product obtained according to Example'7 are dissolved in 50 parts of petroleum ether and parts of pyridineare added. After several hours, the precipitation begins which iscompleted after about hours. It is filtered with suction, washed with asmall quantity of petroleum ether and dried under reduced pressure. Thecolorless hygroscopic solid substance dissolves easily in water andalcohol and dimculty in acetone, ether and petroleum ether. The meltingpoint lies between about 200 C. and about 212 C.

(17) parts of the product obtained according to Example 7 areintroduced, into parts of pyridine in the course 01' about 12 hours, thetemperature being maintained at about 70 C. The product is a yellowishsalvy mass which dissolves in water with a colloidal turbidity.

(18) 54 parts of the chlorine containing compound obtainable accordingto Example '7 are dissolved in parts'of hexahydrobenzene and a solutionof 20 parts of quinoline in 40 parts'oi' hexahydrobenzene is graduallyadded. When the main reaction is finished, the whole is heated to'boiling for about 5 hours, cooled, filtered with wherein R means alkylcontaining from 12 to 14 carbon atoms,- the compound being unstabletowards alkalies and soluble in water.

2. The compound which corresponds with the formula:

iso.CuHu

the compound being unstable towards alkalies and l5 soluble in water. I

3. The compounds corresponding with the general formula I it ammonium 20wherein A stands for a monocyclic aromatic nucleus, R1 stands for alkylhaving at least 4 carbon'atoms, 1!. stands for a member selected fromthe group consisting of 1 and 2, NER stands for a tertiary amine, thecompounds being un- 25 stable towards alkalies.

4. The compounds corresponding with the general formula on III(R1)..L.CH:.N.CI

R1. komi x xn wherein A stands for a monocyclic aromatic nucleus, R1stands ior'alkyl having at least 4 carbon atoms, NER stands for aheterocyclic 45 tertiary amine in which the tertiary nitrogen atom is amember of the nucleus, the compounds being unstable towards alkalies andsoluble in water.

ARNOLD BRUNNER. 60

